Hydrogenation catalyst

ABSTRACT

A hydrogenation catalyst is prepared by: A. providing a hydrocarbon-soluble catalyst precursor which is a reaction product of (a) a transition metal compound (e.g. nickel acetylacetonate) with (b) a phenolic substance (e.g. pnonylphenol); and B. reducing the soluble precursor with (c) an organometallic reducing agent (e.g. n-butyllithium) in a solvent medium to form a highly active catalyst. The catalyst is useful for hydrogenating polyisoprene, EPDM, 1octene, etc.

United States Patent 91 Loveless et a1.

[451 Dec. 17, 1974 1 HYDROGENATION CATALYST [75] Inventors: Frederick C. Loveless, Oakland,

N.J.; Don H. Miller, Warren, Mich.

[73] Assignee: Uniroyal, lnc., New York, N.Y.'

[22] Filed: Feb. 9, 1972 [21] Appl. No.: 224,977

[52] U.S. Cl. 260/80.78, 252/431 R, 252/431 C, 260/821, 260/851, 260/947 H, 260/669 R,

3,412,174 11/1968 Kroll 260/6839 3,625,927 12/1971 Yoshimoto et a1. 260/947 H 3,673,281 6/1972 Bronstert et a1. 260/947 H Primary ExaminerEdward J. Smith Attorney, Agent, or Firm-James .1. Long 1 1 ABSTRACT A hydrogenation catalyst is prepared by:

A. providing a hydrocarbon-soluble catalyst precursor which is a reaction product of (a) a transition metal compound (e.g. nickel acetylacetonate) with (b) a phenolic substance (e.g. p-nonylphenol); and

B. reducing the soluble precursor with (c) an organometallic reducing agent (e.g. n-butyllithium) in a solvent medium to form a highly active catalyst. The catalyst is useful for hydrogenating polyisoprene, EPDM, l-octene, etc,

21 Claims, No Drawings HYDROGENATION CATALYST This invention relates to a hydrogenation catalyst, a method of making same, and a hydrogenation process employing such catalyst.

In one aspect, the invention involves the preparation of a highly active hydrogenation catalyst from a soluble precursor, by subjecting the precursor to the action of an organometallic reducing agent. More particularly, the invention contemplates first providing, as a catalyst precursor, a hydrocarbon-soluble organometallic complex which is a reaction product of (a) an organic chelate compound of a transition metal with (b) a phenolic substance. The thus-formed organometallic complex, or soluble catalyst precursor, is then reduced by the action of (c) an organometallic reducing compound to produce the highly active hydrogenation catalyst.

Considering in more detail ingredient (a) of the soluble catalyst precursor, that is, the organic chelate compound of a transition metal, this is usually a compound of nickel, cobalt or iron with a chelating agent such-as a beta-diketone or a beta-ketoester. Examples of the chelating agents include acetylacetone, 1,3- hexanedione, 3,5-nonadione, methylacetoacetate, ethylacetoacetate and the like.

To arrive at the soluble precursor, the described organic chelate compound of a transition metal (a) is, as indicated, contacted with (b) a phenolic substance, thus producing a soluble organometallic complex. For this purpose phenol itself is suitable, or there may be used a substituted phenol such as a monoalkylphenol having an alkyl group of for example 1 to carbon atoms,,typically in the 2- or 4- position, or a dialkylphenol usually having the alkyl groups (having for example l to 10 carbon atoms in each group) in the 2,4- or 2,6- positions. Examples of such phenols include 2- butylphenol, l-t-butylphenol, 2-octylphenol, 2-toctylphenol, 2-nonylphenol, 4-butylphenol, 4-tbutylphenol, 4-octylphenol, 4-t-octylphenol, 4- nonylphenol, 2-methyl-4-ethylphenol, 2-ethyl-4- butylphenol, 2,4-dipropylphenol, 2,4-di-t-butylphenol, 2-butyl-4-t-octylphenol, 2,4-dinonylphenol, 2-methyl- 6-ethylphenol, 2-ethyl-6-t-butylphenol, 2,6- dipropylphenol, 2,6-di-t-butylphenol, 2-methyl-6-toctylphenol, 2-butyl-6-t-octylphenol, 2,6-

dinonylphenol and the like.

The organometallic soluble catalyst precursor is conveniently made by bringing (a) the transition metal chelate and (b) the phenolic substance together in the presence of an organic solvent medium. For this purpose inert solvents in general are suitable, or, when the material to be hydrogenated is a liquid under the conditions prevailing, such material may be used as the solvent. Frequently the inert solvent is a hydrocarbon solvent, whether saturated (aliphatic, or cycloaliphatic) or aromatic, or combined forms such as hydroaromatic, or mixtures of such solvents may be used. Examples include hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, methylcyclohexane, decalin, tetralin, etc. The solvent may contain, dissolved therein, a material to be hydrogenated. The conditions under which the soluble organometallic complex is formed by interaction of the transition metal chelate and the phenolic material are not critical. Usually the mixing is carried out, with stirring, at somewhat elevated temperature (e.g., 60-9()C) and the reaction is frequently sufficiently completed within a period of dodecyl, phenyl, benzyl, tolyl, cyclopentyl, cyclohexyl,

a few minutes althoughlonger reaction times (e.g., l or 2 hoursor more) may also be used. The organometallic catalyst precursor will remain soluble when the solution is cooled to room temperature. If isolated from the solution it is usually a glassy solid whose color depends upon the transition metal used, but isolation is not necessary. The relative proportions of transition metal chelate to phenolic substance are notcritical and may vary. Usually at least about one-half mole of transition metal chelate is used per mole of phenolic material. Larger quantities may be used, such as for example up to about 2 moles of transition metal chelate per mole of phenolic material. Frequently it is preferred to use approximately equimolar quantities of transition metal chelate and phenolic substance.

Having thus provided the soluble organometallic complex catalyst precursor, the next stage in the method of making the catalyst involves, as indicated, subjecting the precursor to the action of an organometallic reducing agent (c) in the solvent medium. Particularly suitable organometallic reducing compounds are those having the formula MR where M is a metal such as lithium, magnesium or aluminum, R is a hydrocarbon radical, and n is the valence of the metal. The by drocarbon radical R may be saturated (acyclic or cyclic) or aromatic. Especially useful are those compounds in which R has for example up to 12 carbon atoms, as in saturated acyclic hydrocarbon radicals having 1 to 12 carbon atoms, saturated cyclic hydro- 7 carbon radicals having 5 to 12 carbon atoms, and aromatic hydrocarbon radicals having 6 to 12 carbon atoms. Examples of such radicals include alkyl, aryl, alkaryl, aralkyl'and cycloaliphatic groups exemplified by methyl, ethyl, n-propyl, i-propyl, n butyl, i-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl,

and naphthyl radicals. Thus, examples of the organometallic reducing compounds include ethyllithium, npropyllithium, n-butyllithium, i-butyllithium, secbutyllithium, t-butyllithium, n-pentyllithium, phenyllithium, diethylmagnesium, di-n-propylmagnesium, di-nbutylmagnesium, diphenylmagnesium, triethylaluminum, tri-n-propylal'uminum, triisopropylaluminum,

tri-n-butylaluminum, triisobutylaluminum triamylaluminum, trihexylaluminum trioctylaluminum, trididecylaluminum, diethylisobutylaluminum, diethyloctylaluminum tricy- Ordinarily at least about one mole of the reducing compound (c) is employed for each mole of components (a') plus (b). It is frequently preferred to use a molar excess of organic reducing compound (0), for example, the molar amount of compound (c) is advantageously about three times the molar sum of components (a) and (b). A preferred range of (c) in 'two' to five times the sum of (a) and (b). While there is no upper limit to the amount of reducing substance that may be employed, and larger amounts can be used, there is no proportionate added advantage in using such larger amounts and for reasons of economy larger amounts will not ordinarily be used. Slow addition of the reducing compound is preferred since this has been found to assure the formation of a highly active fine dispersion of the reduced metal hydrogenation catalyst. In practice a convenient procedure is to add the reducing agent slowly or in portions with good stirring over a short period of time.

To carry out the hydrogenation process of the invention the substance to be hydrogenated is contacted with hydrogen in the presence of the described catalyst composition. Any organic substance having a nonaromatic hydrogenatable carbon-to-carbon unsaturated bond is operable in the invention, including substances with one or more ethylenic (olefinic) or acetylenic multiple bonds. The hydrogenatable substances include not only low molecular weight or monomeric substances, but also high molecular weight or polymeric substances. Examples of monomeric nonpolymeric materials that may be hydrogenated include unsaturated hydrocarbon monomers, particularly monoolefins having 2 to 12 carbon atoms such as ethylene, propylene, cis-2-butene,. trans-Z-butene, 2- methylbutene-l, Z-methylbutene-Z, l-pentene, 2- pentene, l-hexene, l-heptene, l-octene, isooctene, styrene, vinyl toluene and the like.

Examples of polymers which may be hydrogenated include such unsaturated hydrocarbon polymers as the diene polymers, whether homopolymers or copolymers. Of particular importance are the homopolymers and copolymers of conjugated dienes, including copolymers of conjugated dienes with each other and with copolymerizable ethylenically unsaturated monomers such as the vinyl-substituted aromatic hydrocarbons. Examples of such polymers include polybutadiene, polyisoprene, butadiene-styrene copolymers, butadiene-alpha-methylstyrene copolymers, butadieneisoprene copolymers, polybutadiene grafted with a minor amount of styrene, and others. These polymers may be prepared by bulk polymerization, solution polymerization, or emulsion polymerization by the use of a radical type initiator, an ionic type initiator, or a Ziegler type initiator. The hydrogenated polymers obtained from these polymers are useful for manufacturing rubber articles. In addition to polymers based on conjugated dienes, polymers based on non-conjugated dienes may be used, notably the EPDM class of-polymers. These are ordinarily sulfurcurable, chainsaturated terpolymers of a major proportion of ethyl-.

ene and propylene and a minor amount (sufficient to confer sulfur-vulcanizability) of a non-conjugated diene such as an acyclic diolefin (e.g., 1,4-hexadiene) or a polycyclic diene (e.g., dicyclopentadiene, cyclooctadiene, alkylidene norbornenes ormixtures of such dienes, such as dicyclopentadiene in admixture with ethylidene norbornene, methyl tetrahydroindene, etc.). Usually the preferred EPDM rubbery copolymers contain ethylene and propylene in a weight ratio of from 20:80 to 75:25 and the diene content rangesup to about 20% by weight of the polymer (usually up to 10%). US. Pat. Nos. 2,933,480, Gresham et 211., Apr. 19, 1960; 3,000,866 Tarney, Sept. 19, 1961; 3,063,973, Gladding et al., Nov. 13, 1962; 3,043,620,

1963; and 3,211,709, Adamek et 211., Oct. 12, 1965,

teach examples of suitable alpha-olefin copolymers to which this invention is applicable.

As indicated previously, the substance to be hydrogenated may be present in the solution in which the catalyst is prepared, and, in fact, when the substance to be hydrogenated is a liquid it may itself serve as the solvent. Otherwise, any inert hydrocarbon solvent as previously described may serve as the solvent medium for the hydrogenation. The substance to be hydrogenated is preferably present when the active catalyst is formed by the action of the reducing agent on the soluble precursor. Less preferably the substance to be hydrogenated is added to the solution subsequent to preparation of the catalyst. There are no restrictions on the concentration of the hydrogenatable substance in the solution and such concentration can range all the way from less than 1% by weight up to the limit of solubility, if any, of the hydrogenatable substance in the solvent, all the way to 100% in the case where the hydrogenatable substance itself serves as the solvent. Ordinarily the concentration of the solution of a polymer to be hydrogenated may be varied as desired, for example, from less than 1% to greater than 30%, preferably from about 1 to 20%. The concentration of the solution of a non-polymeric unsaturated compound to be hydrogenated similarly may ordinarily be varied as desired, for example from 1% or less, and higher for those which are solid at room temperature, to about 100% for those which are liquid at the hydrogenation temperature.

The hydrogenation process of the invention is typically carried out by bubbling hydrogen into the solution containing a catalytic amount of the catalyst and the material to be hydrogenated, usually with stirring or shaking depending upon the type of reaction vessel being used. Usually the relative amounts of catalyst and hydrogenatable substance present are such that the mixture contains from about 150 moles or more to 1 moles or less of carbon-to-carbon unsaturation (olefinic double bonds) per mole of transition metal, the preferred amount being about 1 to 20 moles-of carbonto-carbon unsaturation per mole of transition metal. The hydrogenation proceeds under mild hydrogenation conditions, including ambient temperature and pressure. If desired elevated pressure (e.g. l0 atmospheres or higher) may be used for greater efficiency. Typically a convenient pressure range is from about 14 to 50 psig. It is not necessary to exercise special control over the temperature of the reaction mixture, but if desired the mixture may be cooled (e.g., to 10C or less) or heated (e.g. to 100C or more). Frequently the hydrogenation is carried out at a temperature of from 25to 75C. The hydrogenation is rapid and sometimes redesired extent, the catalyst may be deactivated by adding a polar solvent such as acetone or alcohol,preferably containing an excess of mineral acid such as aqueous hydrochloric acid. The hydrogenated substance may be recovered in any suitable conventional manner. In the case of a hydrogenated polymer, addition of the polar solvent ordinarily causes precipitation of the polymer. To prevent any oxidation of the polymer during the recovery operations, a small amount (e.g. 0.25 to 0.75%) of a conventional rubber antioxidant may be added. The extent of hydrogenation of the product may be determined by any of several methods including refractive index, titration, or gas phase chromatography.

In accordance with a preferred practice of the invention the active catalyst-formation step, that is, the step this polyisoprene solution is added 20 ml of the above metal complex solution (equivalent to 16 mmoles of nickel) and the mixture is flushed with hydrogen. To the resultant mixture is added 50 mmole of ninvolving reduction of the dissolved soluble organome- 5 butyllithium as a molar n-heXane Solution dur ng a tallic complex atalyst precursor action of the ga. period Of minutes stirring. The Slow addition of nometallic reducing agent(c), is carried out in the presh reducing e p l results in a ence of hydrogen, and more preferably in the presence h l active mckel hyfiregehahoh Catalyse After h f both hydrogen and the Substance to be hydroge addition of the n-butyllrthrum, the resultant mixture is nated. Such in-situ formation of the active catalyst in 10 contacted wlth hydrogen under a prssure of 14 5 at the hydrogenation mixture insures the formation of a room Fmperature by bubblmg hydrogen catalyst which is highly effective the mixture for a period of 60 minutes. 2,2-

The invention is remarkable for the efficiency with Methylenebm4'methyl'6't'butylphen?l) (qne which otherwise difficult to hydrogenate materials can part, 100 of polymer a polyatherdlamme (reilcilon be hydrogenated. Polyisoprene for example has previ- 15 product of poiypropylene glycol and propylene ously been difficult to hydrogenate. In certain prior hymolgcular welght 2000; three part/100 of polymer) drogenation processes polyisoprene tends to degrade are then added 9 prPtect the pamally hydrogenated but such is not the case in the present process. By use polymer from effluent catalyst Y f the present process polyhutadiehe can be partially moval. The resultant mixture 18 then washedtwrce with hydrogenated to provide an improved material having 20 500 of aqueous hydrchlr 1c acld and the less cold flow and improved gum tensile strength. The polyisoprehe 1S floeulated hy the additloh 0f ahexeess present catalyst is extremely active. The catalyst is not of P PY alcohol Containing 2,2'-methylehe sensitive to small traces of impurities such as water and y p n- The Wet P y Crumb is does not require the vigorous control of reagent ratios dried Overnight at in a Vaeuum Oveh- Analysis of required in certain prior art systems. The catalyst may the P y p using refractive index shows the P ycontain considerable quantities of impurities and comisoprehe to be 45% hydrogehated- The intrinsic Viscosmercial grades of solvents may be used while still mainat 135C in tetrahh of the hydrogenated P y is taining high activity-The present catalyst is superior to compared for the Original P ym The typical prior catalysts in the degree and rapidity of hy- Pe'rimem is summarized as Run 1 in Table 1 dmgenation which is possib|e The experiment demonstrates the outstanding hydro- The following examples will serve to illustrate the gehahoh activity of the Catalyst of this invention at practice f h invention i more d iL room temperature and low hydrogen pressure, without 1 any degradation of the polymer.

' The experiment is repeated, except that the p- EXAMPLE 1 5 nonylphenol is omitted. Analysis of the resultant poly- This example illustrates the preparation of the sulu- Shows y 3% hydrogenation The experiment is ble metal complex using nickel acetyl acetonate as the Summarized 85 Run 2 in Table I. sourcev of the transition metal and the hydrogenation For p p s of pa a'thifd run is made, ability of the catalyst of this invention formed from the dentified 88 Run 3 in Table according to the procesoluble nickel complex. 40 dure of Run 1 but substituting nickel naphthenate for A mixture of 0.24 mole (6L4g) of nick l acetylacthe soluble nickel complex. Run 3 is outside the invenetonate, 0.24 mole (52.8g) of commercial grade ption and employs 400 ml. of a 1% by weight n-hexane nonylphenol and 300 ml. of n-heptane is stirred and solution of polyisoprene using commerical grade nickel heated at 80-90C. for 1 hour. The resultant solution naphthenate as the Source Of the S0luble a s o of the heptane soluble nickel complex is cooled to metal. 15 mmoles of nickel naphthenate is reduced room temperature and stored in a capped bottle. with mmoles of n-butyllithium giving, as indicated 400 ml. of a 2% by weight solution of polyisoprene in Table l, a [RA]/[me] ratio of 3.3 and a [C=C]/[Me] (equivalent to 0.12 moles of olefinic unsaturation calratio of 3.9.. The percent hydrogenation of the polymer culated as moles of monomer or isoprene) in n-hexane as measured by refractive index is 8 percent. The inis placed in a dry 600 ml. narrow neck beverage bottle. 50 trinsic viscosity at 30C in toluene before hydrogena- The polyisoprene is a material sold under the tradetion is 4.16 and after hydrogenation it is 2.53 indicating mark Natsyn 400 by Goodyear Tire and Rubber Co., that a significant amount of polymer degradation has having a Mooney viscosity of (ML-4 at 212F). To occurred.

TABLE 1 Examplel Hydrogenation of Polyisoprene Transition Reducing Mo ar olar Polymer Metal Coma. Ratio Ratio Percent Intrinsic Viscosity Run [Me] Phenol i R Z] [RAl/[Me] [C=C]/[Me] Hydrogenation Before After 1 nickel p-nonyln-butyl- 3 7.3 45 1.07 1.02

acetylphenol lithium (tetralin (tetralin acetonate C) 135C) 2 nickel n-butylacetyllithium 3 7.3 8 acetonate 3 nickel n-butylnaphthenate lithium 3.3 3.9 8 4.16 2.53

. (toluene (toluene 7 EXAMPLE 2 The hydrogenation activity of the catalyst of this invention can be significantly increased by utilizing hydrogen pressures above one atmosphere as demonstrated by the following example. 400 ml. of a 2.5% by weight n-hexane solution of polyisoprene (commercial material known as lsoprene 305," Shell Chemical Co.; 70-90 Mooney viscosity [ML-4 at 2l2F]) was placed in a 500 ml capacity Paar hydrogenation apparatus. A solution of 16 mmoles of soluble nickel complex prepared as in Run 1 of Example 1 was added to the polymer solution. After flushing with hydrogen, 50 mmoles of n-butyllithium was added over a period of minutes and the solution was contacted, while shaking, with hydrogen at 50 psig pressure and room temperature for 60 minutes. The recovered polymer indicated 78% hydrogenation with an intrinsicviscosity of 1.36 as measured in tetralin at 135C. The intrinsic viscosity of the original polymer was 0.81, indicating that hydrogenation resulted in an increase in the molecular weight of the polymer. The experiment is summarized as Run 4 in Table II.

In Run 5, the Run 4 experiment is repeated except that aged catalyst is used, that is, all the catalyst ingredients are combined (in the absence of polyisoprene and hydrogen) and stored for 4 hours in a stoppered bottle at room temperature under a nitrogen atmosphere before use, with the results given in Table ll. Run 5 demonstrates that aging of the catalyst at room temperature for a period up to '4 hours does not have any significant deleterious effect on the hydrogenation capability.

TABLE III Example 3 Hydro enation of Polyisoprene (Run 6) Reaction ime Percent minutes at 75C. Hydrogenation EXAMPLE 4 The following runs (Runs 7, 8, 9 and 10, Table IV) were made to demonstrate the effect of the catalyst level in terms of mmoles of nickel on the hydrogenation of a polymer. The catalyst of this invention was compared with a prior art catalyst made from a soluble nickel salt (nickel naphthenate). The experimental procedure and reaction conditions were the same as in Run 1 of Example 1. The results are summarized in Table IV.

TABLE ll Btample 2 Hydrogenation of Polyisoprene Polymer Transition Reducing lgin of Molar Molar Hydrogen Percent Intrinsic Metal Com;l ata yst Ratio Ratio Pressure Hydro- Viscosity poun Run [Me] Phenol [RA] 7 hrs at RT. [RM/[Me] [C=Cl/[Me] psig genation Before After 4 nickel p-nonyl n-butylacetylphenol lithium 3 9.8 78 0.81 1.36 acetonate 5 nickel p-nonyl n-butylacetylphenol lithium 3 9.8 50 75 0.81 0.97 acetonate TABLE IV Example 4-- Hydrogenation of Polyisoprene Reaction Transition Reducing Molar Molar Time Hydrogen Percent Metalv Corn;i Ratio Ratio Mmoles at 25C pressure Hydro- P Run [Me] Phenol [RA] [RAl/[Me] [C=Cl/ [Me] of Ni Mins. psig genation 7 nickel p-nonyl n-butylacetylphenol lithium 3 l 37 1.56 14 6 acetonate 8 do. do. do. 3.1 3.7 15.6 60 I4 57 9 do. do. do. 0.8 0.93 62.3 60 14 5] l0 nickel naphthenate do. 0.9 62.3 60 I4 25 EXAMPLE 3 EXAMPLE 5 was introduced into a onegallon capacity glass pressure The catalyst of this invention exhibits activity for the hydrogenation oflow-unsaturation, sulfur-vulcanizable EPDM-type elastomer's. Run 1 of Example 1 was repeated using 400 ml of a 2% by weight n-hexane solution of a commercialEPDM elastomer which was a solution polymerized terpolymer of ethylene/propylenel- -ethylidene-2-norbornene (ratio of ethylene to propylene 60:40, by weight), having an iodine number of 28.8, and an intrinsic viscosity in tetralin at 135C of 1.73. The iodine number of the hydrogenated polymer was 1 1.6 indicating that the percent hydrogenation was I EXAMPLE 6 EXAMPLE 7 The following example demonstrates the utility of the catalysts of the present invention in the hydrogenation of low molecular weight alpha-olefin monomers.

Following the procedure of Example 1, soluble metal complexes were made from ferric acetylacetonate and nickel acetylacetonate as indicated in Runs 11 and 13 in Table V. These metal complexes were then used to hydrogenate ml (0.063 moles) of l-octene dissolved in 200 ml of cyclohexane ina 600 ml narrow neck beverage bottle. In each case the metal complex was added to the solution of the alpha-olefin, flushed with hydrogen, and an excess amount of 'n-butyllithium added over a period of 10 minutes. The reaction mixture was then contacted with hydrogen at 14 psig and room temperature for 60 minutes. companion runs without any phenol (Runs 12 and 14, Table V) in the catalyst mixture were run to demonstrate the effect of the unique solubilization action of the phenol. In all cases the reducing agent to transition metal mole ratio was between 6:1 and 10:1. The results are given in Table V.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A process for hydrogenating an organic compound which is a hydrocarbon having an olefinic double comprising contacting, under hydrogenation conditions, said organic compound with hydrogen in the presence of a hydrogenation catalyst in amount effective to catalyze hydrogenation of said organic compound, in an organic solvent medium selected from the group consisting of (i) inert saturated hydrocarbon solvent, (ii) inert aromatic hydrocarbon solvent, and (iii) the said organic compound to be hydrogenated when that compound is a liquid, the said hydrogenation catalyst being produced by the steps of:

LII

A. first forming a hydrocarbon-soluble organometallic complex by contacting, in a hydrocarbon solvent medium,

a. an organic chelate compound of a transition metal selected from the group consisting of nickel, cobalt and iron with a chelating agent selected from the group consisting of beta-diketone and beta-ketoester, with b. a phenolic substance selected from the group consisting of phenol, 2-alkylphenol, 4- alkylphenol, 2,4-dialkylphenol and 2,6- dialkylphenol wherein each alkyl group contains 1 to 10 carbon atoms,

the amount of (a) being from 1% to 2 moles, per mole of (b); and thereafter B. mixing the resulting solution of hydrocarbonsoluble organometallic complex provided in step (A) with c. an organometallic reducing agent of the formula MR where M is a metal selected from the group consisting of lithium, magnesium and aluminum, R is a hydrocarbon radical selected from the group consisting of saturated acyclic hydrocarbon radical having 1 to 12 carbon atoms, saturated cyclic hydrocarbon radical having 5 to 12 carbon atoms and aromatic hydrocarbon radical having 6 to 12 carbon atoms, and n is the valence of the metal M, the amount of (0) being from 1 to 5 moles per combined moles of said organic chelate compound (a) plus said phenolic substance (b), whereby the said hydrogenation catalyst is produced in highly active form as a dispersion of said transition metal in reduced form.

2. A process as in claim 1 in whichthe said material to be hydrogenated is an alpha-olefin monomer.

3. A process as in claim 1 in which the said material to be hydrogenated is a conjugated diene polymer.

4. A process as in claim 3 in which the conjugated diene polymer is a polyisoprene rubber.

5. A process as in claim 1 in which the said material to be hydrogenated is unsaturated ethylenepropylenenon-conjugated diene terpolymer rubber.

6. A process as in claim 1 in which, for every mole of transition metal in said catalyst, there is present sufficient of said substance to be hydrogenated to provide from 1 to 20 moles of oleiinic carbon-to-carbon unsaturation.

7. A process as in claim 1 carried out at a temperature of from 25C to 75C under a pressure of from 14 to 50 psig.

8. A process as in claim 1 in which the said transition I alkylphenol is 4-nonylphenol.

is a saturated acyclic hydrocarbon radical having 1 to 12 carbon atoms.

16. A process as in claim 15 in which the said organometallic reducing agent is n-butyllithium.

17. A process as in claim 1 in which equimolar amounts of (a) and (b) are employed, and the amount of (c) is from 2 to 5 moles per combined moles of (a) plus (b).

18. A process as in claim 1 in which the said step (B) is carried out in the presence of the said organic compound to be hydrogenated and hydrogen.

19. A process for hydrogenating an olefinically unsaturated hydrocarbon polymer selected from the group consisting of conjugated diene polymer and ethylenepropylene-non-conjugated diene terpolymer comprising contacting said polymer with hydrogen at a temperature of from 25C. to 75C. under a pressure of from 14 to 50 psig in a liquid organic solvent medium selected from the group consisting of (i) inert saturated hydrocarbon solvent and (ii) inert aromatic hydrocarbon solvent, in the presence ofa hydrogenation catalyst resulting from the steps of:

A. first forming a hydrocarbon-soluble organometallic complex by contacting, in said solvent medium,

a. an organic chelate of nickel or iron with a betaketoester, with b. a 4-alkylphenol in which the alkyl group contains l to 10 carbon atoms; and thereafter B. mixing the resulting solution of organometallic complex formed in step (A) with c. an organometallic reducing agent which is an alkyllithium having 1 to 12 carbon atoms, the molar amount of (a) and (b) being equal and the amount-of (c) being from 2 to 5 moles per combined moles of (a) plus (b), whereby said hydrogenation catalyst is produced in highly active form as a dispersion of nickel or iron in reduced form, the amount of said polymer to be hydrogenated being sufficient to provide from 1 to 20 moles of olefinic carbon-to-carbon unsaturation for every mole of nickel or iron in the said catalyst.

20. A process as in claim 19 in which the said polymer is polyisoprene.

21. A process as in claim 19 in which the said organic chelate is nickel acetylacetonate, the said 4- alkylphenol is 4-nonylphenol and the said alkyllithium is n-butyllithium. 

1. A PROCESS FOR HYDROGENATING AN ORGANIC COMPOUND WHICH IS A HYDROCARBON HAVING AN OLEFIN DOUBLE COMPRISING CONTACTING, UNDER HYDROCARNONATION CONDITIONS, SAID ORGANIC COMPOUND WITH HYDROGEN IN THE PRESENCE OF A HYDROGENATION CATALYST IN;AMOUNT EFFECTIVE TO CATALLYST HYDEOGENATION OF SAID ORGANIC COMPOUND, IN AN ORGANIC SOLVENT MEDIUM SELECTED FROM GROUP CONSISTINGG OF (I) ;INERT SATURATED HYDROCARBON SOLVENT , (II) INERT AROMATIC HYDROCARBON SOLVENT, AND (II) THE SAID ORGANIC ;COMPOUND IS A LIQUID, THEE SAID HYDROGENATION CATAL POUND IS A LIQUID, THE SAID HYDROGENATION CATALLYST BEING PRODUCED BY THE STEPS OF: A. FIRST FORMING A HYDROCARBON-SOLUBLE ORGANOMETALLIC COMPLX BY CONTACTING, IN A HYDROCARBON SOLVENT MEDIUM, A. AN ORGANIC CHELATE ;COMPOUND OF A TEANSISTION METAL SELECTED FROM THE GROUP CONSISTING OF NICKEL, COBALT AND IRON WITH A CHELATING AGENT SEELECTED FROM THE GROUP B. A PHENOLIC SUBSTANCE SELECTED DROM THE GROUP ING OF PHENOL 2-ALKYLPHENOL, 4-ALKYLPHENOL, 22,4CONSISTING OF BETA-DIKEETONE AND ;BETA-KETOESTER, WITH DIALKYLPHENOL AND 2,6-DIALKYLPHENOL, WHEREIN EACH ALKYL GROUP CONTAINS 1 TO 10 CARBONN ATOMS, THE GROUP OF (A) BEING FROM 1/2 TO 2 MOLES, PER MOLE (B); AND THEREAFTER B. MIXING THE RESULTING SOLUTION OF HYDROCARBONSOLUBLE ORGAOMETALLIC C, AN ORGANOMETALLIC REDUCING AGENT OF THE FORMULA MRN WHERE M IS A METAL SELECTED FROM THE GROUP CONSISTING OF LITHIUM, MAGNESIUM AND ALUMINUM, R IS A HYDROCARBON RADICAL SELECTED FROM THE THE GROUP CONSISTING OF SATURATED ACYLIC HYDROCARBON RADICAL HAVING 1 TO 12 ;CARBON ATOMS, SATURATED CYLIC HYDROCARBON RADICAL HAVING 5 TO 12 CARBON ATOMS ;AND AROMATTIC HYDROCARBON RADICAL HAVING 6 TO 12 CARBON ATOMS ,AND N IS THE VALENCE OF THE METAL M, THE AMOUNT OF (C) BEING FROM 1 TO 5 MOLS PER COMBINED MOLES OF SAID ORGANIC CHELATE COMPOUND (A) PLUS SAID PHENOLIC SUBSTANCE (B) WHEREBY THE SAID HYDROGENATION CATALYST IS PRODUCED IN HIGHLY ACTIVE FORM AS A DISPERSION OF SAID TRANNSITION METAL IN REDUCED FORM.
 2. A process as in claim 1 in which the said material to be hydrogenated is an alpha-olefin monomer.
 3. A process as in claim 1 in which the said material to be hydrogenated is a conjugated diene polymer.
 4. A process as in claim 3 in which the conjugated diene polymer is a polyisoprene rubber.
 5. A process as in claim 1 in which the said material to be hydrogenated is unsaturated ethylenepropylene-non-conjugated diene terpolymer rubber.
 6. A process as in claim 1 in which, for every mole of transition metal in said catalyst, there is present sufficient of said substance to be hydrogenated to provide from 1 to 20 moles of olefinic carbon-to-carbon unsaturation.
 7. A process as in claim 1 carried out at a temperature of from 25*C to 75*C under a pressure of from 14 to 50 psig.
 8. A process as in claim 1 in which the said transition metal is nickel.
 9. A process as in claim 1 in which the said transition metal is iron.
 10. A process as in claim 1 in which the said chelating agent is a beta-ketoester.
 11. A process as in claim 10 in which the said chelating agent is acetylacetone.
 12. A process as in claim 1 in which the said phenolic substance is a 4-alkylphenol.
 13. A process as in claim 12 in which the said 4-alkylphenol is 4-nonylphenol.
 14. A process as in claim 1 in which the said metal M in said organometallic reducing agent is lithium.
 15. A process as in claim 1 in which the said hydrocarbon radical R in said organometallic reducing agent is a saturated acyclic hydrocarbon radical having 1 to 12 carbon atoms.
 16. A process as in claim 15 in which the said organometallic reducing agent is n-butyllithium.
 17. A process as in claim 1 in which equimolar amounts of (a) and (b) are employed, and the amount of (c) is from 2 to 5 moles per combined moles of (a) plus (b).
 18. A process as in claim 1 in which the said step (B) is carried out in the presence of the said organic compound to be hydrogenated and hydrogen.
 19. A process for hydrogenating an olefinically unsaturated hydrocarbon polymer selected from the group consisting of conjugated diene polymer and ethylene-propylene-non-conjugated diene terpolymer comprising contacting said polymer with hydrogen at a temperature of from 25*C. to 75*C. under a pressure of from 14 to 50 psig in a liquid organic solvent medium selected from the group consisting of (i) inert saturated hydrocarbon solvent and (ii) inert aromatic hydrocarbon solvent, in the presence of a hydrogenation catalyst resulting from the steps of: A. first forming a hydrocarbon-soluble organometallic complex by contacting, in said solvent medium, a. an organic chelate of nickel or iron with a beta-ketoester, with b. a 4-alkylphenol in which the alkyl group contains 1 to 10 carbon atoms; and thereafter B. mixing the resulting solution of organometallic complex formed in step (A) with c. an organometallic reducing agent which is an alkyllithium having 1 to 12 carbon atoms, the molar amount of (a) and (b) being equal and the amount of (c) being from 2 to 5 moles per combined moles of (a) plus (b), whereby said hydrogenation catalyst is produced in highly active form as a dispersion of nickel or iron in reduced form, the amount of said polymer to be hydrogenated beiNg sufficient to provide from 1 to 20 moles of olefinic carbon-to-carbon unsaturation for every mole of nickel or iron in the said catalyst.
 20. A process as in claim 19 in which the said polymer is polyisoprene.
 21. A process as in claim 19 in which the said organic chelate is nickel acetylacetonate, the said 4-alkylphenol is 4-nonylphenol and the said alkyllithium is n-butyllithium. 